Light-sensitive color photographic material

ABSTRACT

A new combination of a merocyanine type compound of the formula (I)   wherein R1 is a lower alkyl group; R2 is a lower alkyl, lower alkenyl or aryl group; Z1 represents a non-metallic atom group necessary to complete a 5- or 6-memberd heterocyclic ring nucleus; Z2 represents a non-metallic atom group necessary to complete a 5-membered ring; and n is 0 or 1, in combination with at least one compound of the formula   WHEREIN R4, R5 and R6 are individually a hydrogen atom, or an alkyl, alkenyl, aryl or aralkyl group, and R5 and R6 may be the same or different, is found to be useful in a light-sensitive silver halide color photographic material to improve graininess of the resulting color image when said photographic material is subjected to imagewise exposure to light and color development.

United States Patent 1.

Sakamoto et a1.

[ Aug. 21, 1973 LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 221 Filed: Mar. 19, 1971 21 Appl.No.:126,360

[30] Foreign Application Priority Data Mar. 20, 1970 Japan 45/23143 [52] US. Cl 96/100, 96/109, 96/122, 96/139 [51] Int. Cl G036 l/40, G03c 1/08 [58] Field of Search 96/122, 139, 109, 96/100 [56] References Cited UNITED STATES PATENTS 3,367,780 2/1968 Fix et a1 96/122 3,397,987 8/1968 Luckey et a1. 3,457,078 7/ 1969 Riester 3,480,439 11/1969 Kampfer et a1. 3,563,754 2/1971 Jones et al. 3,580,723 5/1971 Sato et a1 3,615,644 10/1971 Gotze et a1. 96/139 Primary Examiner-J. Travis Brown Att0rneyWaters, Roditi, Schwartz & Nissen [57] ABSTRACT A new combination of a merocyanine type compound of the formula (1) wherein R is a lower alkyl group; R, is a lower alkyl, lower alkenyl or aryl group; Z, represents a nonmetallic atom group necessary to complete a 5- or 6- memberd heterocyclic ring nucleus; Z, represents a non-metallic atom group necessary to complete a 5- membered ring; and n is 0 or 1, in combination with at least one compound of the formula N N N (II) wherein R R and R are individually a hydrogen atom, or an alkyl, alkenyl, aryl or aralkyl group, and R and R may be the same or different, is found to be useful in a light-sensitive silver halide color photographic material to improve graininess of the resulting color image when said photographic material is subjected to imagewise exposure to light and color development.

4 Claims, No Drawings LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL This invention relates to a light-sensitive color photographic material which, when subjected to color development, can give a dye image high in graininess.

For the improvement in graininess of a dye image formed by development of a light-sensitive silver halide color photographic material, there have been known a process in which the silver halide is used in excess, and a process in which a specific chemical is incorporated to lower the color developability of the photographic material. However, the former process has the disadvantage that the silver halide, which is expensive, is required to be used in a large amount to make the production cost of the photographic material high, while the latter process has the disadvantage that the adoption of a special coupler becomes necessary, or otherwise, chemical desensitization is brought about.

With the object of overcoming the above-mentioned disadvantages, we made extensive studies to find that a light-sensitive color photographic material capable of giving a color image excellent in graininess can be obtained by use of a merocyanine type compoundof the formula (l) shown below in combination with a mercaptotetrazole type compound of the formula (ll) Thus, the object of the present invention is to provide a light-sensitive color photographic material capable of giving a color image excellent in graininess by incorporating into the layer of a light-sensitive silver halide emulsion, which has or has not been spectrally sensitized, a merocyanine type compound of the formula wherein R is a lower alkyl group; R, is a lower alkyl, lower alkenyl or aryl group, Z represents a nonmetallic atom group necessary to complete a 5- or 6- membered heterocyclic ring nucleus; Z represents a non-metallic atom group necessary to complete a 5- membered ring; and n is 0 or 1, in combination with a mercaptotetrazole type compound of the formula (II),

3 Exemplified Exemplified compound No. R, R, compound No. [I] Zl C H C H [l] 32 r [l] 33 [I] 23 -CH -CH,CH OCOCH, (H) [l] 24 --CH; CH CH SO K lia lg /C=S o: N Exemplified I 5 compound No.

[l] 34 Exemplified H] 35 compound No. R, R, R, [l] 25 C H C H C,H n 26 --CH,, c,H Q

[l] 27 -CH,, -cH,co0H G (F) f C-N r r i N O: N E n d xemp 1 1e 1 12 30 compound No.

Exemplified compound No. R, R, (I)-38 [I] 28 -CH3 CH5 Q [I] 29 --C;H -C;H,, C H,

I 39 N C O\ H l /C=S 1 I O: N

( JgH5 H l ;:S 1 s O: N

(I)!]. G S H2 =C-S\ HI N /0=s O=G-N Both the compounds of formula (I) and the compounds of formula (ll) may individually be used in combination of two or more. Further, the compounds of formula (I) and the compounds of formula (II) may be incorporated together into one layer or may be incorporated separately into layers adjacent to each other. These compounds may be incorporated not only into emulsion layers but also into such auxiliary layers as sub layers, inter layers or protetive layers. The compounds may be added to silver halides at any stage of the preparation thereof, but are preferably added during second ripening or before coating.

The amounts of the compounds to be added are not particularly limited, and the optimum amounts thereof vary depending on the kinds of the compounds. Generally, however, both the compounds of formula (I) and the compounds of formula (ll) are preferably added in proportions of to 10 mole per mole of AgX. Among the compounds of formulas (l) and (II), those which'are lipophilic may be added in the form of dispersions in a high boiling organic solvent such as dibutyl phthalate or in a low boiling organic solvent such as chloroform, acetone or dimethylformamide, while those which are water-soluble may be added in the form of solutions in a water-miscible organic solvent or in an aqueous alkali solution.

Photographic emulsions used in the present invention may contain AgCl, AgBr, AgClBr, AgBrl, etc. Spectral sensitizing dyes used in the present invention may have been optically sensitized with cyanine dyes or other merocyanine type compounds than those used in the present invention, or may have been subjected to chemical sensitization using sulfur-containing compounds, noble metal salts or polyalkylene oxide derivatives. As hardeners, there may be used formalin and the like, and as coating aids, there may be used synthetic surface active agents or natural surface active compounds, e.g. saponin. Couplers used in a light-sensitive silver halide color photographic material of the present invention are those which form a color image by treatment with p-phenylenediamine type color developing agents, andinclude, for example, yellow couplers having benzoylacetanilide groups, magenta couplers having a pyrazolone or indazolone nucleus, and cyan couplers having a phenol or naphthol nucleus. These couplers may be those which contain in the active methylene or methine positions such substituents as halogens, arylazo groups or aryloxy groups which split ofi upon color development reaction. Further, these couplers may contain in the molecules long chain alkyl groups, alkylphenoxy groups or the like non-diffusible groups, either alone or in combination with sulfonic groups, carboxyl groups or the like water-solubilizing groups. Among these couplers, those which are lipophilic may be used in the form of dispersions in a high boiling organic solvent such as dibutyl phthalate or in a low boiling organic solvent such as chloroform, acetone or dimethylformamide, while those which are watersoluble are dissolved in an alkali, and may be added to silver halide emulsions or may be incorporated into color developing solutions.

The light-sensitive layer of the color photographic material may be composed, for example, either of protective layer, blue sensitive layer, yellow filter layer, green sensitive layer, inter layer, red sensitive layer, anti-halation layer and support, or in this order from the uppermost layer. Sometimes, the green or red sensitive layer may be the uppermost layer. Further, the color development layer may be composed of one or two layers.

The support used in the present invention is ordinarily a paper or a natural or synthetic film of the cellulose acetate or polyester type.

Development of the color photographic material is carried out either in such a manner that a dye image is formed by the primary development, as in the treatment of color negative, or in such a manner that the primary development is effected by using Metol or bydroquinone and then a dye image is formed with a color developer, as in the treatment of reversal color photographic film.

Typical examples of color developing agents used for development of the light-sensitive color photographic material are sulfates, hydrochlorides and sulfites of N,- N-diethyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-ethyl-N-hydroxy-ethyl-2- methyl-p-phenylenediamine and N-ethyl-N-B- methanesulfonamidbethyl-3-methyl-4-aminoaniline.

In order to illustrate wide applications of the present invention, several examples are set forth below, but the invention'is not limited to these examples and various modifications are possible within the scope of the invention.

EXAMPLE 1 (o cmnQo-eH-c oxa- (UCsHn l COCHzCONH (Provided that the coupler dispersion had the composition as set forth below in which the amounts of individual components are per mole of AgX.)

Compositlon of dispersion:

Coupler 180 g. 2,5-Di-(t)-octyl hydroquinone 3 g. Dibutyl phthalate I20 g. Ethyl acetate 300 g. 5% Alkanol B (trade name of 5 a product of Du Pont) 285 ml. 3% Gelatin 2,000 ml.

After mixing the coupler dispersion with the emulsion, 200 ml. of 1 percent formalin and 300 ml. of 5 percent saponin were added to the emulsion. Subsequently, the emulsion was coated on a cellulose triacetate film base to a dry thickness of 5 p. and then dried to prepare a sample. Thereafter, the sample was exposed to a definite amount of light through an optical wedge and then subjected to the following development treatments:

l. Color development; C. 12 minutes.

Composition of developer:

Benzyl alcohol 3.8 ml Anhydrous sodium sulfite 2.0 g. N-Ethyl-N-B-methanesulfon- 20 amidoethyl-3-methyl-4- aminoaniline sulfate 5.0 g. Sodium carbonate 50.0 g. Potassium bromide 1.0 g. Water to make 1,000 ml.

The composition of the fixing solution was the same as in the first fixing. 8. Water-washing; 10 minutes.

As seen in Table 1. it is clear that a photographic material incorporated with both compound (I) and. compound (II) is greatly improved in graininess of the resulting image, without any substantial degradation in speed, as compared with the case where each of the compounds is used singly.

EXAMPLE 2 A high speed silver iodobromide emulsion (containing 4.0 mole percent of Agl, and 160 g. of gelatin per mole of AgX) was subjected to second ripening, and then charged with 1.4 g. (per mole of AgX) of 5- methyl-7-hydroxy-l ,3,4-triazaindolizine and 0.2 g. (per mole of AgX) of a spectral sensitizing dye of the structure shown below to obtain a green-sensitive emulsion. Spectral sensitizing dye:

The thus obtained emulsion was divided into two emulsions. To each of the emulsions, the compound (l)37 was added in the amount as shown in Table 2 Thereafter, a coupler of the structure shown below was formed into two dispersions by means of a high speed rotary mixer.

Coupler:

(0 11111 003,0 ONH 9. Drying. \N/

The relative speed, fog and RMS graininess at a color density value of about 1.0 of the film samplesafter the C1 C1 color development treatments were as shown in Table 1 l. (The RMS (root means square) graininess referred to herein is a value of 1,000 times the standard deviation of density values measured when a uniformly ex- 31 posed and developed sample was scanned by means of a micro-densiwmeter having a micasuring head of 25 I (Provided that the coupler dispersions had such comdlametel) positions as set forth below in which the amounts TABLE 1 Amount of Amount of compound (1) compound ([1) per mole of per mole of Relative Sninplt' AgX AgX speed Fog RMS Control snmplu 100 0.13 116 111-1, 0.15 g... as 0.11 113 Sample of the present invention. [1 1, 0.15 g. {II -4, 0.05 g 110 0. lo

1 -1,0..'-10 g [II --1, 0.05 g 101 0.10 15 I -1, 0.15 g II 4, 0.10 g 95 0.08 15 I -1, 0.15 g H -5, 0.05 g 105 0.10 81 1 -1, 0.15 g [II 7, 0.05 g 100 0.12 85 [I -1, 0.15 g [II -9, 0.05 g 111 0.13 75 1 -1, 0.15 g [II -13, 0.05 108 0.12 so [I -1, 0.15 g [II -1s, 0.10 0.10 85 [I -a, 0.15 g [II -4, 0.05 103 0.08 83 [1 -11, 0.15 [II -1, 0.05 0. 0? s0 1 -17, 0.15 [II -4, 0.05 93 0.14 so [I -2e, 0.15 [II -4, 0.05 117 0.10 85 [I -as, 0.15 [11 4, 0.05 102 0.10 81 of individual components are per mole of AgX.) Compositions of dispersions:

Dispersion l Dispersion 2 Coupler 82 g. 82 g. 2,5-Di-(t)-octyl hydroquinone 3 g. 3 g Compound (ID-l 0.6 g Tricresyl phosphate 60 g. I 60 g Ethyl acetate 250 g. 250 g Alkanol B 320 ml. 320 ml 3% Gelatin 2,000 ml. 2,000 ml.

The coupler dispersions were individually mixed with either of the aforesaid emulsions as shown in Table 2, and then 120 ml. of 1 percent formalin and 300 ml. of 5 percent saponin were added to each emulsion. Subsequently, the emulsions were individually coated on a cellulose triacetate film base to a dry thickness of 5 pt, and then dried to prepare film samples. These film samples were subjected to the same development treatments as in Example 1. The results obtained were as set forth in Table 2.

TABLE 2 Amount of Coupler compound dis- Relative Sample (l)-37 per persion speed Fog RMS mole of AgX No.

Control sample l 100 0.12 105 Sample of the present 0.2 g. 2 97 0.10 76 invention As is clear from Table 2, it is understood that in the case of the color photographic material, the resulting image is greatly improved in graininess without any substantial degradation in speed.

EXAMPLE 3 C1 2H5 cl N N I Calls (EIHG 0.22 g. 0.22 g. Compound (l)-34 0.2 g. Compound (ll)-9 0.08 g. Methyl alcohol 300 ml. 300 ml.

Thereafter, a coupler of the structure shown below was formed into a dispersion by means of a high speed rotary mixer.

O ONH(CH2)( O CsHnUJ Provided that the coupler dispersion had the composition as set forth below in which the amounts of individual components are per mole of AgX. Composition of dispersion:

Coupler 47 g. 2,5'Di(t)-octyl hydroquinone 3 g. Tricresyl phosphate 20 g. Ethyl acetate 130 g. 5% Alkanol B 100 ml 3% Gelatin 2,000 ml.

After mixing the coupler dispersion with each of the emulsions, 50 ml. of 1 percent formalin and 300 ml. of

5 percent saponin were added to each emulsion. Subsequently, the emulsions were individually coated on a cellulose triacetate film base to a dry thickness of 4.5 and then dried to prepare film samples. These samples were subjected to the same development treatments as in Example 1. The results obtained were as set forth in Table 3.

TABLE 3 Sample Emulsion Relative speed Fog RMS Control sample A 0.10 1 l5 Sample of the present invention [05 0.1 l 87 As seen in Table 3, it is understood that in the case of the photographic material, the resulting image is greatly improved in graininess without any substantial variation in speed and fog.

EXAMPLE 4 A high speed silver iodobromide emulsion (containing 4.0 mole percent of Ag], and g. of gelation per mole of AgX) was subjected to second ripening, and then charged with l .4 g. (per mole of AgX) of 5- methyl-7-hydroxy-l ,3,4-triazaindolizine and 0.2 g. (per mole of AgX) of a spectral sensitizing dye of the following structure:

Thereafter, the'thus treated emulsion was divided into several emulsions, which were then individually charged with one or more of compounds (I) and (ll) as shown in Table 4. Subsequently, 57 g. (per mole of AgX) of a coupler of the structure shown below was formed into an alkali dispersion. Coupler:

After mixing the coupler dispersion with each of the emulsions, 100 ml. of 1 percent formalin and 300 ml. of saponin were added to each emulsion. Subsequently, the emulsions were individually coated on a cellulose triacetatefilm base to a thickness of 3 and then dried to prepare samples. These samples were subjected to the same development treatments as in Example 1. The results obtained were as set forth in Table 4.

As seen in Table 4, it is understood that also in the case where two kinds of compounds (I) and one of compound (II), or one of compound (I) and two of compounds (II), are used in combination, the photographic material can be greatly improved in graininess of the resulting image.

EXAMPLE A high speed silver iodobromide emulsion (containing 5.0 mole percent of Ag], and 180 g. of gelatin per mole of AgX) was subjected to second ripening, and then spectrally sensitized by addition of 0.2 g. (per mole of AgX) of the same spectral sensitizing dye as in Example 3. Subsequently, the emulsion was divided into several emulsions, which were then individually charged with one or two of compounds (I) and (II) as shown in Table 5. Thereafter, couplers l and 2 of the structures shown below were formed into a dispersion by means of a high speed rotary mixer.

Coupler I:

CONH(CH;-)r0 06mm) Coupler 2:

OH i

oonmcmn-oQcmmo a nU) -COCH:

(Provided that the coupler dispersion had the composition as set forth below in which the amounts of individual components are per mole of AgX.)

Composition of dispersion:

Coupler I [0 g Coupler 2 4 g. 2,5 Di-(t)-octyl hydroquinone 0.5 g. Tricresyl phosphate 20 g. Ethyl acetate 30 g. 5% Alkanol B 15 ml. 2% Gelatin 400 ml.

After mixing the coupler dispersion with each of the emulsions, ml. of 1 percent formalin and 300 ml. of 5 percent saponin were added to each emulsion. Subsequently, the emulsions were individually coated on a polyester film base to a dry thickness of 3.5 uand then dried to prepare film samples. These film samples were subjected to the same development treatments as in Example l to measure the RMS graininess of the resulting images at the point of color density of 0.3. The results obtained were as shown in Table 5.

TABLE 5 Amount of com- Amouni: of compound (I) per mole pound (II) per mole Relative of AgX of AgX speed Fog RM S 100 0. 08 90 (II)5, 0 08 1: 121 0. 06 89 34 0. 08 9f) (ID-5, O 08 l. 108 0. 08 6'3 010 g A (ID-5, 0 05 t: 0. 08 70 (Il)-5,0.05g.. 106 0408 72 As is clear from Table 5, it is understood that by the combined use of compound (I) and compound (II), the photographic material is greatly improved in graininess of the resulting image.

What we claim is:

l. A light-sensitive silver halide color photographic material comprising one or more layers, at least one of which is a coupler-containin g layer and incorporated in said eouper-containing layer or in a layer adjacent thereto at least one compound of the formula (I),

wherein R is a lower alkyl group; R is a lower alkyl, lower alkenyl or aryl group; Z represents a non metallic atom group necessary to complete a 5- or 6- membered heterocyclic ring nucleus; Z represents a non'metallic atom group necessary to complete a 5- membered ring; and n is 0 or 1, and at least one compound of the formula (II),

R4---N-C--SH wherein R R and R are individually a hydrogen atom, or an alkyl, alkenyl, aryl or aralkyl group, and R and R may be the same or different.

2. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein the combination of said compound (I) and said compound (ll) is incorporated into the coupler-containing layer.

3. A light-sensitive silver halide color photographic material as claimed in claim I, wherein said compound (I) and said compound (ll) are individually incorporated into two different layers which are adjacent to each other.

4. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein each of said compounds (I) and (II) is used in an amount of 10" to 10 mole per mole of the silver halide contained in said photographic material. 

2. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein the combination of said compound (I) and said compound (II) is incorporated into the coupler-containing layer.
 3. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said compound (I) and said compound (II) are individually incorporated into two different layers which are adjacent to each other.
 4. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein each of said compounds (I) and (II) is used in an amount of 10 6 to 10 1 mole per mole of the silver halide contained in said photographic material. 